Plasma-assisted dry etching of noble metal-based materials

ABSTRACT

A process for removing and/or dry etching noble metal-based material structures, e.g., iridium for electrode formation for a microelectronic device. Etch species are provided by plasma formation involving energization of one or more halogenated organic and/or inorganic substance, and the etchant medium including such etch species and oxidizing gas is contacted with the noble metal-based material under etching conditions. The plasma formation and the contacting of the plasma with the noble metal-based material can be carried out in a downstream microwave processing system to provide processing suitable for high-rate fabrication of microelectronic devices and precursor structures in which the noble metal forms an electrode, or other conductive element or feature of the product article.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of co-pending U.S.application Ser. No. 09/453,995, filed on Dec. 3, 1999, which is acontinuation-in part of U.S. application Ser. No. 08/966,797, filed onNov. 10, 1997 and issued on Jan. 25, 2000 as U.S. Pat. No. 6,018,065;and a continuation-in-part of co-pending U.S. application Ser. No.09/093,291, filed on Jul. 8, 1998.

GOVERNMENT RIGHTS IN INVENTION

[0002] Some aspects of this invention were made in the performance ofU.S. Government Contract No. DDALO1-97-C-0079, “BST Capacitors forCryogenic Focal Plane Arrays;” NIST ATP Program, 70NANB9H3018. The U.S.Government has certain rights in the invention hereof.

BACKGROUND OF THE INVENTION

[0003] 1. Field of the Invention

[0004] The present invention generally relates to a process for removalof noble metal-based materials, and more particularly in a preferredaspect to “dry” etching of deposited iridium-based materials tofabricate microelectronic device structures.

[0005] 2. Description of the Related Art

[0006] Iridium (Ir) and iridium oxide (IrO₂) are of great interest foruse as electrode materials in both dynamic random access memories(DRAMs) and for ferroelectric-based memory devices (e.g., FRAMs) thatincorporate perovskite metal oxide thin-films as the capacitor layer.

[0007] The advantages of Ir over other possible electrode materialsinclude ease of deposition, e.g., using chemical vapor deposition (CVD),the ability to “dry” etch the material, the ability to form a stableconducting oxide (IrO₂) at high temperatures in an oxidizingenvironment, the ability to convert IrO₂ back to Ir metal at suitabletemperatures (on the order of 350° C.) in forming gas, and the abilityof the corresponding product microelectronic device to operate stably athigh temperatures with a high degree of reliability.

[0008] The deposition and/or processing of Ir-based electrodes is highlydesirable based on the above-discussed advantages. Ir displays aresistivity 5.3-cm at 20° C. and IrO₂ is highly conducting with areported resistivity of 100-cm. The formation of IrO₂ occurs only atelevated temperatures (>550° C.) in O₂ and is a superior material forthe deposition of complex oxides for dielectric or ferroelectriccapacitors. Further, during the high temperature CVD process for thegrowth of these capacitors, the formation of IrO₂ can be advantageousfor limiting inter-diffusion, as for example by acting as a diffusionbarrier to oxidation of conducting polysilicon vias or plugs. IrO₂therefore is a material having many advantages in forming a robust,low-leakage electrode for reliable device fabrication.

[0009] Based on the need for Ir-based electrodes, a facile etchingmethod for Ir is critical for commercial manufacturing processes,particularly those involving CVD techniques, since CVD enables thefabrication of electrode structures having dimensional characteristicsbelow 0.5 micron.

[0010] In order to obtain useful electrode structures, it generally isnecessary to etch the deposited Ir-based material, to form elements of adesired dimensional and locational character. Heretofore, “dry” etchingtechniques utilizing plasma for reactive ion etching (RIE) have beengenerally chlorine-based and resulted in significant residue being lefton the structure after completion of the etching process.

[0011] Depending on the type of structure being formed, such post-etchresidue can result in short circuiting, undesirable topography and/orother deficiencies in the subsequent operation of the productmicroelectronic device. Prevention of the formation of such residues canbe achieved in some instances by manipulating the reactive ion etching(RIE) process parameters, but such process manipulation producesundesirable sidewall slopes in the microelectronic device structure thatin turn prevent useful submicron capacitors from being fabricated fromiridium-based materials.

[0012] Accordingly, it would be a significant advance in the art offabricating microelectronic devices and precursor structures therefor,to provide a simple and commercially useful “dry” etch methodologyapplicable to Ir-based materials that provides high etching rates,superior etching uniformity and effective control over the shape of theetched features.

SUMMARY OF THE INVENTION

[0013] The present invention relates in one aspect to a method forremoving residue from or “dry” etching a noble metal material previouslydeposited on a substrate, such as a microelectonic device, by contactingthe deposited material with a gas-phase composition comprising at leastone energized halogenated organic and/or inorganic compound or mixturethereof, thereby etching or removing the deposited material to yield adesired structure formed of the noble metal material, e.g., an electrodeor other structural component or feature of a microelectronic device.

[0014] The gas-phase composition or plasma contacting is advantageouslycarried out in an “oxidizing ambient environment” for a sufficient timeand under sufficient conditions to effectively etch the deposited noblemetal material or remove noble metal residue, thereby reducingdeficiencies in the operation of the microelectronic device.

[0015] The method of the present invention is usefully employed foretching or removing noble metal materials including, without limitation,platinum, palladium, iridium, rhodium and materials comprising alloys orcombinations of such metals, as well as alloys or combinations of one ormore of such metals with other (non-noble) metal. Most preferably, thenoble metal material is an iridium-based material.

[0016] As used herein, the term “Ir-based” or “iridium-based” refersbroadly to elemental iridium, iridium oxide and iridium-containingmaterial compositions including iridium alloys. As used herein, the term“microelectronic device structure” refers to a microelectronic device,or a precursor structure that must be subjected to subsequent processingor treatment steps to fabricate a final product device.

[0017] As used herein, the term “dry” etch refers to etching that iscarried out using gaseous reagents, as opposed to wet-etching methods inwhich liquid-phase reagents are employed to effect material removal froma deposited metal thin film, or layer of material. The “dry” etchprocess of the present invention is a plasma etching process. A “plasma”is a highly ionized gas with a nearly equal number of positive andnegative charged particles plus free radicals. The free radicals areelectrically neutral atomic or molecular species that can actively formchemical bonds.

[0018] In the plasma etching process or residue removal process of thepresent invention, free radicals generated in a plasma and acting as areactive species, chemically combine with materials to be etched orremoved and form volatile compounds that are readily removable from thesystem, e.g., by an evacuating device joined in closed flowcommunication with the plasma etch chamber.

[0019] The reactive etching reagent may include, for example, at leastone halogenated compound selected from an organic halogenated compound,such as C₂F₆; inorganic halogenated compound, such as XeF₂ and SF₆ or amixture of halogenated organic and inorganic compounds, such as C₂F₆ andXeF₂, and an oxidizing gas to a sufficient amount of energy to generatereactive species sufficiently energized to etch the depositediridium-based material upon contact therewith.

[0020] The halogenated organic compounds that are useful as “startingmaterial” for plasma generation to form the etching medium, can compriseany compound that will effectively provide, upon energizing, a reactivehalogenated etching gas. Suitable halogenated organic compounds usefulin specific applications of the plasma etching process include, withoutlimitation, alkyl halides having an alkyl moiety selected from C₁-C₆alkyl species, with at least some and preferably all of the hydrogensubstituents of the alkyl moiety being replaced by halogen. Specificexamples of alkyl halides include, without limitation, CF₄, C₂F₆,C₂Cl₃F₃, C₄F₈, C₅F₈, C₃F₈, C₂Cl₂F₄, C₂ClF₃, CClF₃, CCl₃F, CCl₂F₂, etc.,with C₂F₆ being a particularly preferred alkyl halide species. Thehalogenated organic compound can include any suitable halogensubstituent, e.g., fluorine, bromine, chlorine, or iodine, with fluorinegenerally being the most preferred.

[0021] In one aspect, an etching gas mixture is employed for the etchingof the noble metal-based material, in which the etching gas mixtureincludes (i) at least one halogenated organic compound and (ii) at leastone gas that provides an “oxidizing ambient environment” to assist inthe volatilization and removal of iridium product species from theiridium-based material on the substrate.

[0022] As used herein, the term “oxidizing ambient environment” means anenvironment including oxygen-containing gas, such as oxygen (O₂), ozone(O₃), air, nitrogen oxide (NO), nitrous oxide (N₂O), carbon monoxide(CO) or the like, and preferably O₂. Such oxidizing atmosphere may beprovided in a processing chamber with the introduction of thehalogenated organic compound into the chamber to effect the etching ofthe noble metal-based material.

[0023] In one specific embodiment of the dry plasma etching process, theproduct etched structure, such as for example an electrode or othercomponent of a microelectronic device, is formed with a microwave orradio frequency (RF)-generated etching plasma. Any suitable RF ormicrowave radiation may be used for plasma generation. In one embodimentof such process, the halogenated compound(s), in an oxidizing ambientenvironment, is energized in a RF-processing system to produce theplasma for the etch operation.

[0024] In another embodiment of the present invention, the productetched structure is formed with a microwave-generated etching plasma.Any suitable microwave radiation may be used for plasma generation.

[0025] Other aspects, features and embodiments of the invention will bemore fully apparent from the ensuing disclosure and appended claims.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS THEREOF

[0026] The present invention is based on the discovery that noblemetal-based materials, e.g., iridium, platinum, palladium, and rhodiumand based electrode structures, can be readily formed into a desiredconfiguration by employing a “dry” etch processing technique on thenoble metal-based material, e.g., by utilizing reactive etching gasescomprising halogenated organic and/or inorganic compounds in anoxidizing ambient environment.

[0027] While the ensuing discussion herein is sometimes hereinafterdirected illustratively to iridium as the noble metal forming thedeposit to be etchingly altered, it will be appreciated that theinvention is not thus limited in utility, but that the inventioncontemplates plasma etching generally of noble metal-based materials, ofwhich iridium is a widely used species for fabrication of electrodes andother conductive elements and features of microelectronic devicearticles and precursor structures.

[0028] Accordingly, with reference to iridium as a noble metal speciesillustrative of the method of the invention, the iridium initially canbe deposited on the substrate in any suitable manner, including chemicalvapor deposition, liquid delivery, sputtering, ablation, or any othersuitable technique known in the art for deposition of such metal on asubstrate from a metal organic or other precursor or source material.Among the foregoing techniques, chemical vapor deposition is preferredwhen the iridium-based structures to be formed have critical dimensionsbelow about 0.5 microns. In the deposition of Ir-based materials on asubstrate by chemical deposition methods, the precursor for the chemicalvapor deposition of the iridium component may be any suitable iridiumprecursor compound, complex, or composition that is advantageous foryielding iridium during the deposition process.

[0029] Prior to contacting of the deposited noble metal-based materialon the substrate, the noble metal may be masked, or patterned, e.g., byconventional photoresist or other patterning technique(s), to form alithographically or otherwise defined pattern for subsequent etchprocessing.

[0030] Etching of the deposited Ir-based material is carried out bycontacting the deposited iridium-based material with a reactive etchingreagent. The reactive etching reagent may include, for example, at leastone halogenated compound selected from an organic halogenated compound,such as C₂F₆; inorganic halogenated compound, such as XeF₂ and SF₆ or amixture of halogenated organic and inorganic compounds, such as C₂F₆ andXeF₂, and an oxidizing gas to a sufficient amount of energy to generatereactive species sufficiently energized to etch the depositediridium-based material upon contact therewith. The contacting of thedeposited Ir-based material with the reactive species is carried out fora sufficient time and under sufficient conditions to form an etchedsurface structure of the desired configuration.

[0031] The dry clean process of the present invention may be carried outat any suitable process conditions, including ambient temperature, lowtemperature and elevated temperature regimes, as well as varyingpressure regimes. For example, the cleaning process may be carried outat room temperature conditions involving the sublimation of XeF₂ togenerate same as an active cleaning agent. XeF₂ may also be firstreacted with another compound, such as silicon, to generate an activecleaning agent comprising SiF₂ radicals.

[0032] The time and contacting conditions for the reactive halide etchprocess may be readily determined by those of ordinary skill in the art.The nature and extent of the etching of the deposited noble metal-basedmaterial may be empirically determined while varying the time and/orcontacting conditions (such as temperature, pressure, and concentration(partial pressure) of the etching agent to identify the processconditions producing a desired etching result.

[0033] The halogenated organic compound can comprise any compound thatwill effectively provide, upon energizing, a reactive halogenatedetching gas. The halogenated organic compound can include, for example,one or more alkyl halides, e.g., C₁-C₆ alkyl halides such as CF₄, C₂F₆,C₂Cl₃F₃, C₄F₈, C₅F₈, C₃F₈, C₂Cl₂F₄, C₂ClF₃, CClF₃, CCl₃F, CCl₂F₂, etc.,with C₂F₆ being highly preferred as a source halocompound to form theetching medium. The halogenated organic compound may comprise anysuitable halogen substituent(s), e.g., fluorine, bromine, chlorine,and/or iodine, with fluorine generally being the most preferred. Thehalogenated organic compound may be partially or fully halogenated, withfully (halo)substituted compounds being preferred, andperfluorocompounds being most preferred.

[0034] Advantageously, especially in the case of iridium and/or iridiumoxide as the noble metal on the substrate, the etching gas mixtureincludes the halogenated organic compound in combination with at leastone oxygen-containing gas, to assist in the volatilization and removalof iridium product species from the iridium-based material on thesubstrate. The oxygen-containing gas may include, for example, one ormore of O₂, O₃, N₂O, CO, NO, etc. Preferably, the oxygen-containing gasis 02, O₃ or a mixture thereof.

[0035] While not wishing to be bound by any specific theory ofoperation, it is believed that the inclusion of an oxygen-containing gasmay be advantageous with the use of halogenated organic compounds, toreduce the amount of free carbon available (by reaction of carbonaceousspecies with the oxygen-containing gas to form CO and CO₂).

[0036] This substantially prevents any formed polymeric by-products fromdepositing on the interior surface of the chamber or the etchedsurfaces. Additionally, any formed CO gas is available to increase etchrates; for example, in applications where the halo species, X=chlorineor bromine, the presence of CO gas serves to enhance the reactantvolatility through the formation of (CO)_(y)IrX₃ and Ir(Cl)₄.

[0037] The source gas mixture for the etchant medium therefore comprisesa halogenated organic compound, e.g., C₂F₆, and an oxidizing gas, e.g.,O₂, and may be energized in any suitable manner, such as in a RF ormicrowave processing system.

[0038] There are two fundamental types of microwave plasma processingsystems, the oven type and the downstream type. The oven type microwaveplasma processing system provides a single chamber wherein the plasmagenerating and reacting regions are combined. The article to be etchedis placed in the single chamber and exposed not only to the generatedplasma but also to the radiation source. Alternatively, and preferably,a downstream type of microwave plasma processing system, havingseparated generating and reaction regions, is employed, wherein theworkpiece is placed outside of the plasma generating region in thedownstream reacting region. This downstream processing type of microwaveplasma processing system is preferred because the workpiece is notexposed to the electromagnetic radiation necessary to energize theetching gases.

[0039] Owing to the fact that downstream microwave plasma processing ispreferred in the general practice of the invention when microwaveenergization of the source gas(es) is employed for plasma formation, theensuing description in respect of plasma processing refers to thepreferred downstream microwave processing.

[0040] In the plasma processing system, the illustrative reactive gasmixture of C₂F₆ and O₂, whose components may be added eithersimultaneously or separately to the process chamber, is introduced tothe plasma generating chamber and ionized by microwave to form a plasma.The continuous volumetric flow ratio of C₂F₆ to O₂ in such process canfor example be on the order of from about 100 to about 0.1, and morepreferably from about 4 to about 0.5.

[0041] Radicals generated in the plasma generating region of themicrowave processing chamber are subsequently introduced into thereacting region of the processing chamber to react with the Ir-basedmaterial. The distance between the generating and reacting region may bevaried depending on the etch requirements and the specific systemvariables involved. By way of illustration, such distance may forexample be on the order of from about 8 mm to about 600 mm dependent onthe active life of the radicals.

[0042] Some radicals are long-lived and are capable of surviving manycollisions (with other particles and the walls of the chamber) whilemaintaining sufficient energy to reach the reacting region. Otherradicals are not as stable, and as such decay before reaching thereacting region. As a result, when using a mixture of gases containingboth long- and short-lived radicals, the distance between the generatingand reacting regions will desirably be adjusted accordingly.Advantageously, in the present invention, the use of C₂F₆ as a sourcematerial for the etchant medium tends to extend the active life of theO₂ radicals, thereby accommodating the provision of a moderate distancebetween the generating and reacting regions, e.g., a spacing distance inthe range of from about 150 mm to about 600 mm.

[0043] In the microwave processing system, the plasma is typicallygenerated in the preferred gas mixture of C₂F₆ and O₂ at a pressure inthe range of from about 0.005 Torr to about 2 Torr by electromagneticradiation having a frequency in the range of from about 1×10⁸ Hz toabout 1×10¹² Hz.

[0044] If an RF processing system is utilized, the plasma is typicallygenerated by electromagnetic radiation having a frequency in the rangeof from about 1×10³ Hz to about 1×10¹² Hz, more preferably in a rangefrom about 1×10⁵ Hz to about 1×10⁸ Hz, and most preferably, theelectromagnetic radiation is about 400 KHz.

[0045] The process gas mixture and processing conditions required toetch the Ir-based material typically depend on the etching features andshape of the product structure. The time and contacting conditionsadvantageously employed in a specific end use application of theinvention may be readily determined by those of ordinary skill in theart, by the simple expedient of empirical determination of the etchingof the deposited Ir-based (or other noble metal-based) material whilevarying the time and/or contacting conditions such as temperature,pressure, concentration of the etching agent, etc., to provide thedesired results.

[0046] Generally, the process gas mixture comprising C₂F₆ and O₂ gasesis introduced into the plasma processing system continuously at asuitable flow rate to maintain a continuous source of energizedradicals. Typically, a suitable flow rate for the introduction of thegases into the plasma generating region ranges from about 200 sccm toabout 1000 sccm, however, actual flow rates will be dependent on thevolume of the reactor chamber and as such the above flow rates areillustrative only, and are not to be limitingly construed.

[0047] During the etching process, the Ir-based substrate may suitablybe maintained at an appropriate temperature, e.g., a temperature rangingfrom about 0° C. to about 100° C., and more preferably from about 20° C.to about 50° C.

[0048] The plasma energized halogenated organic compounds may furthercomprise the reaction product of an initial reaction, e.g., reactingC₂F₆ with O₂ to form COF₂.

[0049] In one embodiment, at least one halogenated compound selectedfrom an organic compound, such as C₂F₆; inorganic halogenated compound,such as XeF₂, SF₆; SiF₄, Si₂F₆, Si₂OF₆, and radicals SiF₂ and SiF₃; ormixture of halogenated organic and inorganic compounds, such as C₂F₆ andXeF₂ may be used as a gas-phase reactive halide composition or anetching gas to assist in the volatilization and removal of a noblemetal, such as an iridium species from an iridium-based materialdeposited on a substrate.

[0050] In another embodiment, at least one halogenated compound selectedfrom an organic halogenated compound, such as C₂F₆; inorganichalogenated compound, such as XeF₂ and SF₆ or a mixture of halogenatedorganic and inorganic compounds, such as C₂F₆ and XeF₂ may be used as anetching gas wherein the halogenated compound is reacted with elementalsilicon or quartz substrates in the presence of O₂ or O₃, and theresultant active products, including for example, SiF₄, Si₂F₆, Si₂OF₆,and radicals SiF₂ and SiF₃, may be used as an etching gas, to assist inthe volatilization and removal of iridium species from the iridium-basedmaterial on the substrate. Radicals SiF₂ and SiF₃ may further begenerated by passing SiF₄ through an energetic dissociation source,wherein the energetic dissociation source is selected from the groupconsisting of a plasma source, an ion source, an ultra violet source anda laser source.

[0051] Preferably, the etching gas compositions lack nitrogen-and/orphosphorous-containing compounds, such as nitrogen- and/orphosphorous-containing -acceptor ligands to prevent interaction of the-acceptor ligands with the silicon or etching surface. When thesilicon-containing active species are generated by interaction with thehalogenated organic and/or inorganic compounds during the etchingprocess, it is believed that highly volatized iridium species are formedthat may include iridium-silicon halide complexes that are generallydescribed as IrX₁, IrX₃, /IrX₄and/or IrX₆ (where X=silicon halidecomplex), and more specifically Ir(SiF₂)_(x), where x=1, 2, 3 or 4, suchas IrSi₂F₄, IrSi₃F₆ and/or IrSi₄F₆. It is believed that if the etchingcomposition comprises nitrogen- and/or phosphorous-containing species,such as nitrogen-and/or phosphorous-containing -acceptor ligands, thatare in proximity to the etching surface the nitrogen-and/orphosphorous-containing species will interact with other components inthe composition or with the resultant volatized species and reduce theeffectiveness of the etching or the volatility of the volatized species.

[0052] In another aspect of the invention, iridium may be removed from amicroelectronic device structure by contacting the microelectronicdevice structure with a gas-phase reactive halide comprising XeF₂ and anagent to assist in volatilizing, such as a Lewis-based adduct orelectron back-bonding species. The agent is selected from the groupconsisting of carbon monoxide, trifluorophosphine, andtrialkylphosphines to accelerate the rate of etching by enhancing thevolatility of the etch by-products and noble metal (halide)x species ornoble metal (halide radical)x species.

[0053] The microelectronic device structure is contacted with thereactive halide and agent for a sufficient time to at least partiallyremoving the iridium metal residue from the microelectronic devicestructure.

[0054] In yet another aspect of the invention, the iridium-containingfilm prior to its formation, as an electrode structure, may havedeposited thereon a high temperature dielectric and/or ferroelectricmaterial. This is usually accomplished in an oxidizing environment. Assuch the oxidizing ambient environment may be employed not only duringdeposition of the oxide dielectric/ferroelectric, but may also be usedduring the subsequent etching process for forming the electrodestructure.

[0055] In addition to the etching of a deposited Ir-based material as anIr-based electrode structure, it is contemplated that etching processesin accordance with the present invention may be used to clean an Ir CVDchamber to reduce particle formation and contamination therein.

[0056] The etching methods of the present invention may also be employedin etching Ir-based material deposited on or over a high temperaturedielectric material or ferroelectric material, so that the Ir-basedmaterial serves as a top electrode structural material, as well as ahard mask layer to pattern the underlying dielectric or ferroelectricmaterial.

[0057] The dielectric or ferroelectric material may comprise anysuitable material for the specific end use or application beingcontemplated. Examples of potentially useful materials include SBT, PZT,BST, PLZT, PNZT, and LaCaMnO₃.

[0058] The etching methods of the present invention may be utilized foriridium films deposited for the formation of electrode and otherelements of semiconductor devices, such as for example DRAMs, FRAMs,hybrid systems, smart cards and communication systems, as well as anyother applications in which the thin films of iridium and/or iridiumoxide, or combinations thereof, are advantageously employed.

[0059] The features and advantages of the invention are more fully shownby the following non-limiting example. This example illustrates oneembodiment of the present invention involving etching of Ir-basedmaterials deposited on a substrate to form Ir-based material structuresthereon. As discussed hereinabove, methods in accordance with thepresent invention may be usefully employed to form etched metalstructures deriving from a variety of noble metal-based materials.

EXAMPLE 1

[0060] An Ir-based material layer approximately 40 nm thick wasdeposited on a quartz crystal microbalance disk and placed on a supportin the reacting chamber of a downstream microwave processing system.

[0061] A mixture of process gases including C₂F₆ and O₂ in a volumetricflow ratio (such ratio being a dimensionless value, wherein thevolumetric flow rate of each of the respective halocarbon and oxidantgases is measured in the same units, e.g., of standard ft³/minute) of 1was continuously introduced into the microwave plasma generating regionat a flow rate of approximately 1,100 sccm.

[0062] A plasma was formed from the process gases using a microwaveplasma generator and the resultant plasma then was introduced into thereacting region of the plasma system. The etching process was performedfor approximately 25 minutes, which was a sufficient time to completelyremove the Ir-based material from the quartz crystal microbalancesubstrate.

[0063] While the invention has been described herein with reference tospecific features, aspects and embodiments, it will be recognized thatthe invention may be widely varied, and that numerous other variations,modifications and other embodiments will readily suggest themselves tothose of ordinary skill in the art. Accordingly, the ensuing claims areto be broadly construed, as encompassing all such other variations,modifications and other embodiments, within their spirit and scope.

What is claimed is:
 1. A plasma-assisted dry etching method for etchinga noble metal material, said method comprising: contacting the noblemetal material, in the presence of an oxidizing agent selected from thegroup consisting of oxygen and ozone, with an energized plasmacomposition comprising etch species from at least one halogenatedcompound selected from the group consisting of organic halogenatedcompounds, inorganic halogenated compounds and mixtures thereof, forsufficient time to at least partially etch said noble metal material,wherein the energized plasma composition contacting the noble metalmaterial lacks nitrogen- and phosphorous-containing species.
 2. Themethod according to claim 1 , wherein the noble metal material comprisesan Ir-based material.
 3. The method according to claim 2 , wherein theetch species comprise C₂H₆ in the presence of O₂.
 4. The methodaccording to claim 1 , wherein the energized plasma is energized byelectromagnetic radiation.
 5. The method according to claim 4 , whereinthe electromagnetic radiation has a frequency ranging from about 1×10³to about 1×10¹² Hertz.
 6. The method according to claim 5 , wherein thenoble metal material comprises Ir.
 7. The method according to claim 4 ,wherein the noble metal material comprises IrO₂.
 8. The method accordingto claim 3 , wherein the energized plasma further comprises aco-reactant to assist in the volatilization and removal of iridiumproducts from the Ir-based material.
 9. The method according to claim 8wherein the co-reactant is selected from the group consisting ofelemental silicon and quartz.
 10. The method according to claim 3 ,wherein the etch species further comprises XF₂.
 11. The method accordingto claim 1 , wherein the oxidizing gas comprises an oxidant selectedfrom the group consisting of O₂, and O₃.
 12. The method according toclaim 2 , wherein the energized plasma is energized in a downstreammicrowave processing system.
 13. The method according to claim 12 ,further comprising the removing at least one iridium product in thecourse of the etching process.
 14. The method according to claim 1 ,wherein the halogenated organic compound comprises a compound selectedfrom the group consisting of C₂F₆, C₂Cl₃F₃, C₄F₈, C₅F₈, C₃F₈, C₂Cl₂F₄,C₂ClF₃, CClF₃, CCl₃F and CCl₂F₂.
 15. The method according to claim 14 ,wherein the halogenated organic compound comprises C₂F₆ in combinationwith the halogenated inorganic compound XeF₂.
 16. The method accordingto claim 15 , wherein the energized plasma further comprises reactivespecies formed by reacting C₂F₆ with elemental silicon.
 17. The methodaccording to claim 16 , further comprising the removal of at least oneiridium product during the etching process.
 18. The method according toclaim 17 , wherein the at least one iridium product comprises aniridium-containing composition selected from the group consisting ofIrSi₂F₄, IrSi₃F₆, and IrSi₄F₆.
 19. The method according to claim 16 ,wherein the oxidizing gas comprises O₂.
 20. The method according toclaim 2 , wherein the Ir-based material is deposited on a hightemperature dielectric material or ferroelectric material.
 21. A methodof fabricating a microelectronic device structure, comprising:depositing a noble metal material on a substrate; forming a pattern onthe deposited noble metal material of a desired configuration;contacting the deposited noble metal material in the presence of anoxidizing gas selected from the group consisting of oxygen and ozone,with an energized plasma comprising etch species deriving from at leastone halogenated compound selected from the group consisting of organichalogenated compounds, inorganic halogenated and mixtures thereof, tothereby etch the noble metal material, wherein the energized plasmacomposition contacting the noble metal material lacks nitrogen-andphosphorous-containing species; and continuing step (c) for a sufficienttime and under sufficient conditions to form the microelectronic devicestructure or a precursor thereof.
 22. The method according to claim 21 ,wherein the noble metal material comprises an Ir-based material.
 23. Themethod according to claim 21 , wherein the etch species comprise C₂H₆ inthe presence of O₂.
 24. The method according to claim 23 , the energizedplasma is energized by electromagnetic radiation.
 25. The methodaccording to claim 22 , wherein the electromagnetic radiation has afrequency ranging from about 1×10³ to about 1×10¹² Hertz.
 26. The methodaccording to claim 25 , wherein the energized plasma further comprises aco-reactant to assist in volatilization and removal of iridium productsfrom the Ir-based wherein the co-reactant is selected from the groupconsisting of elemental silicon and quartz.
 27. The method according toclaim 21 , wherein the oxidizing gas includes an oxidant selected fromthe group consisting of O₂, and O₃.
 28. The method according to claim 23, wherein the energized plasma further comprises XeF₂.
 29. The methodaccording to claim 26 , further comprising removing at least one iridiumproduct during the etching process.
 30. The method according to claim 21, wherein the halogenated organic compound comprises a compound selectedfrom the group consisting of C₂F₆, C₂Cl₃F₃, C₄F₈, C₅F₈, C₃F₈, C₂Cl₂F₄,C₂ClF₃, CClF₃, CCl₃F and CCl₂F₂.
 31. The method according to claim 22 ,wherein the halogenated organic compound comprises C₂F₆.
 32. The methodaccording to claim 31 , wherein the energized plasma further comprisesreactive species formed by reacting C₂F₆ with a co-reacting speciesselected from the group consisting of elemental silicon and quartz. 33.The method according to claim 32 , further comprising removal of atleast one iridium product in the etching process.
 34. The methodaccording to claim 33 , wherein the at least one iridium productcomprises an iridium composition selected from the group consisting ofIrSiF₃ IrSi₂F₄, IrSi₃F₆, and IrSi₄F₆.
 35. A method for removing a noblemetal residue from a microelectronic device structure, the methodcomprising: contacting the microelectronic device, having depositedthereon a noble metal residue selected from the group consisting ofplatinum, palladium, iridium and rhodium, with a gas-phase reactivecomposition comprising a halide component selected from the groupconsisting of SF₆, SiF₄, Si₂F₆, SiF₂ radical and SiF₃ radical, in anamount to remove noble metal residue from the microelectronic devicestructure, in the presence of an oxidizing gas selected from the groupconsisting of oxygen and ozone, wherein the gas-phase reactivecomposition lacks nitrogen-and phosphorous-containing species.
 36. Themethod according to claim 35 , wherein the halide is selected from thegroup consisting of SF₆, SiF₄, and Si₂F₆.
 37. The method according toclaim 35 , wherein the halide comprises SF₆.
 38. The method according toclaim 35 , wherein the halide is selected from the group consisting ofSiF₂ and SiF₃ radicals.
 39. The method according to claim 35 , whereinthe halide is selected from the group consisting of SiF₂ and SiF₃radicals and the halide is generated by reaction of XeF₂ with silicon.40. The method according to claim 35 , wherein the halide is selectedfrom the group consisting of SiF₂ and SiF₃ radicals and the halide isgenerated by passing SiF₄ through an energetic dissociation source. 41.The method according to claim 40 , wherein the energetic dissociationsource is selected from the group consisting of plasma sources, ionsources, ultraviolet sources and laser sources.
 42. A method forremoving from a microelectronic device structure, a noble metal residuecomprising iridium, the method comprising: contacting themicroelectronic device structure with a gas-phase reactive halidecomprising XeF₂ and an agent to assist in volatilizing and at leastpartially removing the noble metal residue from the microelectronicdevice structure.
 43. The method according to claim 42 , wherein theagent is selected from the group consisting of carbon monoxide,trifluorophosphine, and trialkylphosphines.
 44. The method according toclaim 43 , wherein the agent further comprises an iridium halide speciesselected from the group consisting of Ir(X)₁, Ir(X)₃, Ir(X)₄ and Ir(X)₆,wherein X represents the halide of the reactive halide composition. 45.The method according to claim 42 , wherein, the gas-phase reactivehalide composition further comprises a gas phase reactive halide speciesselected from the group consisting of SiF₄, Si₂F₆, SiF₂ radical and SiF₃radical; and the microelectronic device structure is further contactedwith an agent to assist in volatilizing and removing the noble metalresidue on the microelectronic device structure.
 46. The methodaccording to claim 42 , wherein the agent is selected from the groupconsisting of Lewis bases and electron back-bonding species.
 47. Themethod according to claim 42 , further comprising disposing themicroelectronic device structure in a chamber and introducing a gasphase reactive halide composition selected from the group consisting ofSF₆, SiF₄ and Si₂F₆ that is continuously flowed through the chamber, incombination with an energetic dissociation source selected from thegroup consisting of plasma sources, ion sources, ultraviolet sources andlaser sources.
 48. The method according to claim 42 , further comprisingdisposing the microelectronic device structure in a chamber andintroducing a gas phase reactive halide composition selected from thegroup consisting of SiF₂ and SiF₃ that is continuously flowed throughthe chamber, in combination with an energetic dissociation sourceselected from the group consisting of plasma sources, ion sources,ultraviolet sources and laser sources.
 49. A method for removing from amicroelectronic device structure a noble metal residue including atleast one metal selected from the group consisting of platinum,palladium, iridium and rhodium, the method comprising: contacting themicroelectronic device structure with a gas-phase reactive compositioncomprising SiF₄ in a sufficient amount to at least partially removenoble metal residue.
 50. A method for removing from a microelectronicdevice structure a noble metal residue including at least one metalselected from the group consisting of platinum, palladium, iridium andrhodium, the method comprising: contacting the microelectronic devicestructure with a gas-phase reactive halide composition comprising Si₂F₆in a sufficient amount to at least partially remove noble metal residue.51. A method for removing from a microelectronic device structure anoble metal residue including at least one metal selected from the groupconsisting of platinum, palladium, iridium and rhodium, the methodcomprising contacting the microelectronic device structure with agas-phase reactive halide composition comprising a halide componentselected from the group consisting of SF₆, SiF₄, Si₂F₆, SiF₂ radical,SiF₃ radical, and XeF₂, in an amount effective to at least partiallyremove the noble metal residue; the gas-phase composition (a) furthercomprising an oxidizing gas selected from the group consisting of oxygenand ozone, and (b) lacking a nitrogen- and phosphorous-containingspecies.